Electrical methods are effective tools for the characterization of oil-contaminated sites and are applied in defining the geometry of the contaminated plume and in designing the remedial process. The optimal methodology integrates geoelectric methods, data processing, and interpretation techniques. Electromagnetic profiling is a reliable and fast method used to provide the configuration of oil-contaminated plume from apparent resistivity map and used to guide the subsequent electrical resistivity tomography survey. From advanced field work methods, data processing, and interpretation procedures, electrical resistivity tomography survey provides the three-dimensional (3D) configuration of the contaminated plume, migration pathways, location of active contaminated sources, and information about lithology. For separate contaminated and clean zones, a petrophysical modeling is used for the calculation of soil resistivity based on groundwater salinity. Taking the pore-water salinity value into account, an inversion algorithm recalculates resistivity maps into maps of clay content, porosity, and cation exchange capacity, allowing a more accurate determination of the volume of contaminated soil. From clay content data, hydraulic conductivity values are calculated for determining the groundwater vulnerability due to vertical migration of contaminants from upper layers. The optimal geoelectric methodology is an efficient procedure to assess hydrocarbon-contaminated sites, with emphasis on large sites with deeper groundwater table.